Amorphous UiO-66 Synthesis via Mild Coordination

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Solution Overview

Problem

Current methods for synthesizing amorphous UiO-66 require high temperature, high pressure, mechanical ball milling, and chemical corrosion, making it impossible to prepare under cell survival conditions for biological applications.

Innovation Solution

A method involving the heating mixing of polyethylene glycol (PEG), zirconium nitrate, and water to form a metal solution, followed by the heating mixing of ammonium fluoride, terephthalic acid, and water to form a ligand solution, which are then combined and subjected to coordination at mild temperatures (15° C. to 37° C.) under normal pressure to produce amorphous hierarchically porous UiO-66.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Stability of the object's composition

If conventional methods (high temperature, high pressure, mechanical ball milling, chemical corrosion) are used to prepare amorphous UiO-66, then amorphous structure is achieved, but the preparation conditions are harsh and toxic solvents are required

Engineering Contradiction:
Improveamorphous structureVSAvoidharsh preparation conditions and toxic solvents
Core Design Contradiction:
Stability of the object's compositionVSObject-affected harmful factors

Solution Approach 1:

The patent changes the preparation parameters from high temperature/high pressure to mild temperature (15-37°C) and normal pressure, achieving amorphous UiO-66 under biocompatible conditions through controlled coordination polymerization in aqueous solution

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses polyethylene glycol (PEG) as a mediator to facilitate the coordination between zirconium ions and terephthalic acid, enabling amorphous structure formation under mild conditions without requiring toxic solvents or extreme conditions

Inventive Principle:
Principle #24Intermediary (Mediator)

2Stability of the object's composition

If high temperature and high pressure are applied to convert crystalline MOFs to amorphous MOFs, then amorphous structure is obtained, but energy consumption increases

Engineering Contradiction:
Improveamorphous structureVSAvoidenergy consumption
Core Design Contradiction:
Stability of the object's compositionVSUse of energy by moving object

Solution Approach 1:

The patent dramatically reduces the energy input parameters from high temperature/high pressure to mild temperature (15-37°C) and normal pressure, achieving amorphous UiO-66 through solution-phase coordination polymerization that requires minimal energy input

Inventive Principle:
Principle #35Parameter changes

3Stability of the object's composition

If conventional synthesis methods are used for amorphous UiO-66, then amorphous structure is achieved, but biocompatibility is lost

Engineering Contradiction:
Improveamorphous structureVSAvoidbiocompatibility
Core Design Contradiction:
Stability of the object's compositionVSAdaptability or versatility

Solution Approach 1:

The patent changes the preparation conditions to biocompatible parameters including physiological temperature range (15-37°C), normal pressure, aqueous solution environment, and absence of toxic solvents, enabling potential biomedical applications of amorphous UiO-66

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent employs polyethylene glycol (PEG) as a biocompatible mediator that facilitates the formation of amorphous structure under physiological conditions, making the material suitable for biomedical applications

Inventive Principle:
Principle #24Intermediary (Mediator)

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This method allows for the preparation of amorphous hierarchically porous UiO-66 under mild conditions, avoiding high energy consumption and toxic solvents, and enabling biocompatibility for potential applications in the biomedical field.

Implementation Method 1

PEG shows high hydrophilicity, and ethoxy repeating unit in the PEG interacts with Zr4+, thus promoting coordination self-assembly of metal ions and organic ligands

Methodology Applied
Scientific EffectCoordination: Chemical Bonding

Implementation Method 2

The coordination is achieved through chemical bonding between the metal ions and carboxyl oxygen atoms, thereby forming preliminary coordination polymer structures

Methodology Applied
Scientific EffectCoordination: Chemical Bonding

Implementation Method 3

in which water molecules act as a medium to help the metal ions and organic ligands ligate in space

Methodology Applied
Scientific EffectSolvation: Solvation

Data Source

PatentUS12338132B1Method for preparing amorphous hierarchically porous UiO-66
Publication Date: 2025.06.24 SHENZHEN POLYTECHNIC
  • US12338132B1 patent drawing
  • US12338132B1 patent drawing
  • US12338132B1 patent drawing

AI summary

A method for preparing an amorphous hierarchically porous UiO-66 is provided. Ammonium fluoride is added to promote dissolution of terephthalic acid (TPA) in water, and then zirconium nitrate is dissolved in water. Polyethylene glycol (PEG) shows high hydrophilicity, and ethoxy repeating unit in the PEG interacts with zirconium ions, thus promoting coordination self-assembly of metal ions and organic ligands. The zirconium ions react with carboxyl groups of the TPA through coordination. The coordination is achieved through chemical bonding between the zirconium ions and carboxyl oxygen atoms, thereby forming preliminary coordination polymer structures. As the coordination proceeds, these preliminary coordination polymer structures begin to self-assemble into short-range ordered network structures, in which water molecules act as a medium to help the zirconium ions and organic ligands ligate in space, thereby generating the amorphous hierarchically porous UiO-66.